Hydrosilylation Catalyzed by Base Metals

Sunada, Yusuke; Nagashima, Hideo

doi:10.1002/9783527814787.ch11

Cited by 10 publications

(12 citation statements)

References 99 publications

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“…2 The transition-metal-catalyzed hydrosilylation of unsaturated bonds is regarded as an efficient and straightforward strategy for forging versatile organosilanes in a perfect atom- and step-economic fashion. 3 Compared to other transition-metal catalysts (TMs), the earth-abundant and low-toxicity first-row TMs (such as Fe, Co and Ni) show high and unique reactivity and are of great interest and significance. 4…”

Section: Introductionmentioning

confidence: 99%

Regiodivergent hydrosilylation in the nickel(0)-catalyzed cyclization of 1,6-enynes

et al. 2022

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Section: Introductionmentioning

confidence: 99%

Regiodivergent hydrosilylation in the nickel(0)-catalyzed cyclization of 1,6-enynes

et al. 2022

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“…For instance, catalysts using precious metals, such as Rh, Ir, Ru, and Pt, have been developed. However, alternative, abundant base metals, such as Fe, Co, and Mn, have recently attracted attention and have been used as hydrosilylation catalysts . In comparison to that on iron and manganese catalysts, the research on cobalt catalysts has been less advanced …”

Section: Introductionmentioning

confidence: 99%

“…(0.23 g, 42%). 1 H NMR (C 6 D 6 ): δ 14.27 (s, 1 H, OH), 8.41(d, J = 4.6 Hz, 1 H, Py), 7.91 (s, 1 H, NCH), 7.31 (d,…”

mentioning

confidence: 99%

Homoleptic Cobalt(II) Phenoxyimine Complexes for Hydrosilylation of Aldehydes and Ketones without Base Activation of Cobalt(II)

et al. 2021

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Air-stable, easy to prepare, homoleptic cobalt(II) complexes bearing pendant-modified phenoxyimine ligands were synthesized and determined. The complexes exhibited high catalytic performance for reducing aldehydes and ketones via catalytic hydrosilylation, where a hydrosilane and a catalytic amount of the cobalt(II) complex were added under base-free conditions. The reaction proceeded even in the presence of excess water, and excellent functional-group tolerance was observed. Subsequent hydrolysis gave the alcohol in high yields. Moreover, H2O had a critical role in activation of the Co(II) catalyst with hydrosilane. Several additional results also indicated that the cobalt(II) center acts as an active catalyst in the hydrosilylation of aldehydes and ketones.

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“…Alkene hydrosilylation has received sustained attention from chemists for over 50 years because it leads to many useful products containing C–Si bonds . Early alkene hydrosilylation catalysts used Co as the central metal, though Co catalysts have been supplanted by more robust Pt catalysts that remain the most used catalysts in practice. , However, growing attention to sustainable chemistry has sparked a renaissance of Co-based hydrosilylation catalysts . Since Deng and co-workers reported an NHC silyl Co catalyst in 2013, numerous Co alkene hydrosilylation catalysts have been reported in the literature in the past few years …”

Section: Introductionmentioning

confidence: 99%

Mechanistic Study of Alkene Hydrosilylation Catalyzed by a β-Dialdiminate Cobalt(I) Complex

et al. 2020

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Alkene hydrosilylation is a large-scale process that typically uses precious-metal catalysts. A new generation of highly selective catalysts is based on inexpensive metals, which may have a high-spin electronic configuration and thus may follow novel mechanistic pathways. Here, we describe mechanistic studies on a high-spin cobalt(I) catalyst that performs rapid and regioselective alkene hydrosilylation. Using 1-hexene and PhSiH 3 as substrates, we elucidate features of the rate law, test for free radical intermediates with radical clock substrates, and use deuterium substitution to provide mechanistic insight. The resting state has PhSiH 3 bound η 6 through the phenyl group and evolves over the course of the reaction from a substrate-bound form to a product-bound form. This complicates analysis by variable time normalization analysis (VTNA) because the dependence of the rate on [PhSiH 3 ] is not constant throughout the reaction. Despite this challenge, the accumulated results are consistent with initial oxidative addition of PhSiH 3 , followed by alkene binding, and then insertion through the Chalk−Harrod or modified Chalk− Harrod mechanism to form the hydrosilylation product. Though the catalyst has a paramagnetic metal center, none of the data implicate radicals participating in the mechanism, and a conventional electron-pair mechanism is most consistent.

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Hydrosilylation Catalyzed by Base Metals

Cited by 10 publications

References 99 publications

Regiodivergent hydrosilylation in the nickel(0)-catalyzed cyclization of 1,6-enynes

Regiodivergent hydrosilylation in the nickel(0)-catalyzed cyclization of 1,6-enynes

Homoleptic Cobalt(II) Phenoxyimine Complexes for Hydrosilylation of Aldehydes and Ketones without Base Activation of Cobalt(II)

Mechanistic Study of Alkene Hydrosilylation Catalyzed by a β-Dialdiminate Cobalt(I) Complex

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